Composition for forming low dielectric thin film including siloxane monomer or siloxane polymer having only one type of stereoisomer and method of producing low dielectric thin film using same

Abstract

Disclosed herein is a composition for forming a low dielectric thin film, which includes silane monomers having only any one of stereoisomer, or a siloxane polymer produced by polymerizing the monomers, and a method of producing the low dielectric thin film using the same. When using the composition, mechanical properties are excellent because tacticity of a matrix is improved, and formation of pores is increased due to a molecular free volume, thus it is possible to produce a low dielectric thin film having low dielectricity.

1. A composition for forming a low dielectric thin film, comprising:
 organosilicon monomers, comprising a monomer of a single type of stereoisomer; 
 a porogen; 
 a solvent, 
 an acid or a base; and 
 water. 
 
     
     
       2. The composition as set forth in  claim 1 , wherein the composition comprises 1-70 wt % siloxane monomers and up to 50 wt % porogen. 
     
     
       3. The composition as set forth in  claim 1 , wherein each of the siloxane monomers is one type of monomer selected from the group consisting of a multi-reactive cyclic siloxane monomer represented by following Formula 1, a Si monomer represented by following Formulas 2 or 3, and a linear alkoxy silane monomer represented by following Formulas 4 or 5: 
       
         
           
           
               
               
           
         
       
       wherein R 1  is a hydrogen atom, C 1  to C 3  alkyl group, or C 6  to C 15  aryl group, R 2  is a hydrogen atom, C 1  to C 10  alkyl group, or SiX 1 X 2 X 3 , wherein X 1 , X 2 , and X 3  are independently a hydrogen atom, C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a halogen atom, wherein at least one of functional groups, R 1  and R 2 , is a hydrolyzable group; and m is an integer from 3 to 8; 
       
         
           
           
               
               
           
         
       
       wherein R is a hydrogen atom, C 1  to C 3  alkyl group, C 3  to C 10  cycloalkyl group, or C 6  to C 15  aryl group, X 1 , X 2 , and X 3  are independently C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a halogen group, n is an integer from 3 to 8, and m is an integer from 1 to 10;
   X 3 X 2 X 1 Si-M-SiX 1 X 2 X 3   Formula 3 
 
       wherein X 1 , X 2 , and X 3  are independently a hydrogen atom, C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a halogen atom, wherein at least one of X 1 , X 2 , and X 3  is a hydrolyzable functional group; and M is a single bond, C 1  to C 10  alkylene group, or an arylene group having 6 to 15 carbon atoms;
   (R 1 ) n Si(OR 2 ) 4-n   Formula 4 
 
       wherein R 1  is a hydrogen atom, C 1  to C 3  alkyl group, a halogen group, or C 6  to C 15  aryl group, R 2  is a hydrogen atom, C 1  to C 3  alkyl group, or C 6  to C 15  aryl group, wherein at least one of R 1  and OR 2  is a hydrolyzable functional group; and n is an integer from 0 to 3; and 
       
         
           
           
               
               
           
         
       
       wherein R 1  is a hydrogen atom, C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a hydroxy or halogen atom, wherein at least one of said groups is a hydrolyzable functional group; and n is an integer from 0 to 30. 
     
     
       4. The composition as set forth in  claim 1 , wherein each of the siloxane monomers is one type of monomer selected from the group consisting of siloxane monomers represented by the following Formulas 6, 7, 8, 9, 10, 11, and 15: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       5. The composition as set forth in  claim 1 , wherein the siloxane monomers including only one type of stereoisomer are cis-type siloxane monomers. 
     
     
       6. The composition as set forth in  claim 1 , wherein the siloxane monomers including only one type of stereoisomer are trans-type siloxane monomers. 
     
     
       7. The composition as set forth in  claim 1 , wherein the porogen is selected from the group consisting of polycaprolactone, α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. 
     
     
       8. The composition as set forth in  claim 1 , wherein the porogen is a surfactant selected from the group consisting of sulfate, sulfonate, phosphate, carboxylic acid, an alkyl ammonium salt, a gemini surfactant, a cetyl ethyl piperidinium salt, dialkyl dimethyl ammonium, a BRij-based surfactant, primary amine, poly(oxyethylene) oxide, octaethylene glycol monodecyl ether, octaethylene glycol monohexadecyl ether, octylphenoxy polyethoxy(9-10) ethanol, and a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer. 
     
     
       9. The composition as set forth in  claim 1 , wherein the solvent is selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone-based solvent, an ether-based solvent, an acetate-based solvent, an alcohol-based solvent, an amide-based solvent, a silicon-based solvent, and a mixture thereof. 
     
     
       10. The composition as set forth in  claim 1 , wherein an acid catalyst is hydrochloric acid, nitric acid, benzene sulfonic acid, oxalic acid, or formic acid, and a base catalyst is potassium hydroxide, sodium hydroxide, triethylamine, sodium bicarbonate, or pyridine. 
     
     
       11. A composition for forming a low dielectric thin film, comprising:
 organosilicon monomers having only one type of stereoisomer; 
 a solvent, 
 an acid or a base; and 
 water. 
 
     
     
       12. A composition for forming a low dielectric thin film, comprising:
 1-70 wt % siloxane polymer, which is produced by polymerizing siloxane monomers, comprising a monomer of a single type of stereoisomer; 
 0-50 wt % porogen; and 
 a solvent. 
 
     
     
       13. The composition as set forth in  claim 12 , wherein the siloxane polymer is produced by hydrolyzing and polycondensating one or more monomers which include only one type of stereoisomer selected from the group consisting of monomers represented by the following Formulas 1 to 5 in an organic solvent in the presence of an acid or base catalyst and water: 
       
         
           
           
               
               
           
         
       
       wherein R 1  is a hydrogen atom, C 1  to C 3  alkyl group, or C 6  to C 15  aryl group, R 2  is a hydrogen atom, C 1  to C 10  alkyl group, or SiX 1 X 2 X 3 , wherein X 1 , X 2 , and X 3  are independently a hydrogen atom, C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a halogen atom, wherein at least one of functional groups, R 1  and R 2 , is a hydrolyzable group; and m is an integer from 3 to 8; 
       
         
           
           
               
               
           
         
       
       wherein R is a hydrogen atom, C 1  to C 3  alkyl group, C 3  to C 10  cycloalkyl group, or C 6  to C 15  aryl group, X 1 , X 2 , and X 3  are independently C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a halogen group, n is an integer from 3 to 8, and m is an integer from 1 to 10;
   X 3 X 2 X 1 Si-M-SiX 1 X 2 X 3   Formula 3 
 
       wherein X 1 , X 2 , and X 3  are independently a hydrogen atom, C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a halogen atom, wherein at least one of X 1 , X 2 , and X 3  is a hydrolyzable functional group; and M is a single bond, C 1  to C 10  alkylene group, or an arylene group having 6 to 15 carbon atoms;
   (R 1 ) n Si(OR 2 ) 4-n   Formula 4 
 
       wherein R 1  is a hydrogen atom, C 1  to C 3  alkyl group, a halogen group, or C 6  to C 15  aryl group, R 2  is a hydrogen atom, C 1  to C 3  alkyl group, or C 6  to C 15  aryl group, wherein at least one of R 1  and OR 2  is a hydrolyzable functional group; and n is an integer from 0 to 3; and 
       
         
           
           
               
               
           
         
       
       wherein R 1  is a hydrogen atom, C 1  to C 3  alkyl group, C 1  to C 10  alkoxy group, or a hydroxy or halogen atom, wherein at least one of said groups is a hydrolyzable functional group; and n is an integer from 0 to 30. 
     
     
       14. The composition as set forth in  claim 12 , wherein the siloxane polymer is produced by hydrolyzing and polycondensating one or more monomers which include only one type of stereoisomer selected from the group consisting of monomers represented by the following Formulas 6, 7, 8, 9, 10, 11, and 15 in an organic solvent in the presence of an acid or base catalyst and water: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       15. The composition as set forth in  claim 12 , wherein the siloxane polymer is produced by polymerizing only cis-type siloxane monomers. 
     
     
       16. The composition as set forth in  claim 12 , wherein the siloxane polymer is produced by polymerizing only trans-type siloxane monomers. 
     
     
       17. The composition as set forth in  claim 12 , wherein the porogen is selected from the group consisting of polycaprolactone, α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. 
     
     
       18. The composition as set forth in  claim 12 , wherein the porogen is a surfactant selected from the group consisting of sulfate, sulfonate, phosphate, carboxylic acid, an alkyl ammonium salt, a gemini surfactant, a cetyl ethyl piperidinium salt, dialkyl dimethyl ammonium, a BRij-based surfactant, primary amine, poly(oxyethylene) oxide, octaethylene glycol monodecyl ether, octaethylene glycol monohexadecyl ether, octylphenoxy polyethoxy(9-10) ethanol, and a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer. 
     
     
       19. The composition as set forth in  claim 12 , wherein the solvent is selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a ketone-based solvent, an ether-based solvent, an acetate-based solvent, an alcohol-based solvent, an amide-based solvent, a silicon-based solvent, and a mixture thereof. 
     
     
       20. A method of producing a low dielectric thin film, comprising:
 applying the composition according to  claim 1  on a substrate; and 
 hardening the resulting composition. 
 
     
     
       21. A method of producing a low dielectric thin film, comprising:
 applying the composition according to  claim 12  on a substrate; and 
 hardening the resulting composition. 
 
     
     
       22. The method as set forth in  claim 20 , wherein the application is conducted using spin coating, dip coating, spray coating, flow coating, or screen printing. 
     
     
       23. The method as set forth in  claim 21 , wherein the application is conducted using spin coating, dip coating, spray coating, flow coating, or screen printing. 
     
     
       24. The method as set forth in  claim 20 , wherein the hardening is conducted by heating at 150-600° C. for 1-180 min. 
     
     
       25. The method as set forth in  claim 21 , wherein the hardening is conducted by heating at 150-600° C. for 1-180 min. 
     
     
       26. A semiconductor interlayer insulating film produced using the composition according to  claim 1 . 
     
     
       27. A semiconductor interlayer insulating film produced using the composition according to  claim 12 .